U.S. patent application number 13/124271 was filed with the patent office on 2011-11-03 for photo-crosslinkable antifouling compositions, films obtained from said compositions, and corresponding uses.
This patent application is currently assigned to CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS). Invention is credited to Claude Bunel, Irene Campristron, Claire Hellio, Rachid Jellali, Albert Laguerre, Jean-Luc Mouget, Jean-Francois Pilard.
Application Number | 20110268689 13/124271 |
Document ID | / |
Family ID | 40668114 |
Filed Date | 2011-11-03 |
United States Patent
Application |
20110268689 |
Kind Code |
A1 |
Bunel; Claude ; et
al. |
November 3, 2011 |
PHOTO-CROSSLINKABLE ANTIFOULING COMPOSITIONS, FILMS OBTAINED FROM
SAID COMPOSITIONS, AND CORRESPONDING USES
Abstract
Photo-crosslinkable antifouling compositions, in particular
antibacterial, antifungal and anti-algae ones, which include the
combination of at least one telechelic oligoisoprene of a
particular formula with an agent for crosslinking the
oligoisoprene. The antifouling film is obtained by applying a thin
layer of such a liquid composition on a substrate and is
crosslinked at room temperature by exposure to visible and/or UV
radiations. The film can be used for preventing the occurrence of a
biofilm on any surface in a humid or aqueous environment, and can
be used as an additive for preparing materials with a view to
imparting bacteriostatic and/or bactericidal properties
thereto.
Inventors: |
Bunel; Claude; (Rouen,
FR) ; Campristron; Irene; (Le Mans, FR) ;
Hellio; Claire; (Concarneau, FR) ; Jellali;
Rachid; (Le Mans, FR) ; Laguerre; Albert; (Le
Mans, FR) ; Mouget; Jean-Luc; (Le Mans, FR) ;
Pilard; Jean-Francois; (Pance, FR) |
Assignee: |
CENTRE NATIONAL DE LA RECHERCHE
SCIENTIFIQUE (CNRS)
Le Mans Cedex 9
FR
UNIVERSITE DU MAINE
|
Family ID: |
40668114 |
Appl. No.: |
13/124271 |
Filed: |
October 8, 2009 |
PCT Filed: |
October 8, 2009 |
PCT NO: |
PCT/FR09/51924 |
371 Date: |
July 21, 2011 |
Current U.S.
Class: |
424/78.09 ;
424/78.31; 428/336; 522/170; 522/186 |
Current CPC
Class: |
C08F 2/50 20130101; C09D
4/00 20130101; C08K 5/0025 20130101; A01N 37/06 20130101; C08K 5/07
20130101; C09D 123/22 20130101; A01N 43/20 20130101; A01N 33/12
20130101; Y10T 428/265 20150115; C08K 5/06 20130101; C08K 5/11
20130101; A01N 31/02 20130101; C08L 2666/02 20130101; C09D 123/22
20130101 |
Class at
Publication: |
424/78.09 ;
428/336; 522/186; 522/170; 424/78.31 |
International
Class: |
A61K 31/745 20060101
A61K031/745; C08F 2/46 20060101 C08F002/46; A01P 1/00 20060101
A01P001/00; B32B 3/00 20060101 B32B003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 14, 2008 |
FR |
0805680 |
Claims
1. Photo-cross-linkable antifouling composition, in particular
antibacterial, antifungal and/or antalgic, characterized in that it
includes the combination of at least one telechelic oligoisoprene
of general formula (I): ##STR00026## or such an oligoisoprene (I)
partially hydrogenated, of formula (II): ##STR00027## or a
partially epoxidized compound of formula (I), of formula (III):
##STR00028## in which formulas: n is an integer between 5 and 100,
preferably between 8 and 70 m and p are integers, less than n,
preferably such that m<p<n R.sub.1 is a group chosen from:
OH, C.sub.1 to C.sub.12 alkoxy, aryloxy, acryloyl,
--NR.sub.3R.sub.4 with R.sub.3 being H or a C.sub.1-C.sub.12 linear
alkyl and R.sub.4 being H or a C.sub.1-C.sub.12 linear alkyl
R.sub.2 is a group chosen from: OH, acryloyl, --NR.sub.5R.sub.6 or
--N.sup.+R.sub.5R.sub.6R.sub.7 with R.sub.5 and R.sub.6, identical
or different, being chosen from: H, alkyl, hydroxyalkyl, cyanoalkyl
and halogenoalkyl in C.sub.1-C.sub.12, in which R.sub.7 is a
C.sub.6-C.sub.15 linear alkyl, and at least one cross-linking agent
of said telechelic oligoisoprene.
2. Composition according to claim 1, characterized in that the
oligoisoprene is in liquid or at a temperature of between 5 and
35.degree. C.
3. Composition according to claim 1, characterized in that it also
includes a photo-cross-linkable reactive diluent.
4. Composition according to claim 1, characterized in that it
consists exclusively of the combination of at least said telechelic
oligoisoprene of formula (I), (II) or (III) and at least one
cross-linking agent of said telechelic oligoisoprene.
5. Composition according to claim 1, characterized in that it also
contains constituents not involved in photo-cross-linking, such as
dyes, pigments, active principles, metal particles, magnetic
particles, reinforcing agents.
6. Antifouling film, characterized in that it is obtained by
applying a thin film of a liquid composition according to claim 1
onto a support and cross-linked by visible and/or ultraviolet
radiation.
7. Film according to claim 6, characterized in that it has biocidal
or biostatic properties with respect to bacteria, fungi, microalgae
and/or macroalgae.
8. Support coated with a film according to claim 6, characterized
in that the total thickness of the film is between around 10 .mu.m
and 500 .mu.m.
9. A method of inhibiting the appearance of a biofilm on medical
instruments, catheters or implants, on walls in contact with an
aqueous medium or in a moist environment, such as floor covering
surfaces, external walls, pipelines, or cooling tours, comprising
applying the antifouling film according to claim 6 to said medical
instruments, catheters, implants, walls, floor covering surfaces,
external walls, pipelines, or cooling tours.
10. A method of conferring bacteriostatic and/or bactericidal
properties to materials comprising adding the composition of claim
1 to said materials.
11. The method according to claim 10, wherein said materials are
selected from the group consisting of medical instruments,
biomaterials, catheters, prostheses and implants.
12. The method according to claim 10, wherein said materials are
coverings or packaging containers, in particular in the agrifood
field.
13. A method for the antifouling protection of a support immersed
in freshwater or seawater, comprising applying to said support the
antifouling film according to claim 6.
14. The method of claim 13, wherein the support is a watercraft
hull.
Description
[0001] This invention relates to cross-linkable antifouling and in
particular antibacterial, antifungal and antalgic compositions, the
films obtained from these compositions as well as the use of these
films in particular for antifouling protection of surfaces immersed
in a freshwater environment and in a seawater environment.
[0002] The phenomenon of fouling corresponds to spontaneous
colonization and accumulation of microorganisms, algae and animals
on surfaces immersed for a variable period of time in a freshwater
environment or in a seawater environment. Fouling is a significant
nuisance, in particular for watercraft, because by deteriorating
the surface of the hulls, it leads to an increase in maintenance
costs and presents resistance to the forward movement of the
watercraft, resulting in overconsumption of fuel and a reduction in
speed.
[0003] To overcome this phenomenon, paints incorporating
tributyltin, a very effective biocide, have been used for a number
of years. Unfortunately, this molecule and its degradation
products, released in the seawater environment, seriously affect
ecosystems, which has resulted in their total prohibition since
2008. In addition, these residues, including tin, remain in the
sediments of ports and immersion sites of dredged slurry.
[0004] By replacing tributyltin, a certain number of products that
are in principle less toxic have been used: these are for the most
part biocidal molecules of low molecular weight such as halogenated
molecules, for example chlorinated derivatives (sold under the
names: Seanine 211, Kathon 5287, Dichlofluanid, Daconil, Thiodan,
Duron, etc.), metal-based derivatives such as zinc or copper (Zinc
pyrithione, Ziram, Dithane, etc.) or nitrogenated heterocyclic
derivatives (Irgarol 1051), which are incorporated in the matrix of
the coating.
[0005] These molecules are, however, slowly released into the
aquatic environment, thus producing, by accumulation, a certain
toxicity in the environment. The European program REACH encourages
abandonment of the addition of any organic product (of the
herbicide or pesticide type, such as the derivatives described
above) in the antifouling paint formulations. In addition,
silicone-based paints have been developed, and admittedly
demonstrate efficacy in the antifouling field, but have limited
applicability, in particular due to their high production
costs.
[0006] An objective of this invention is to propose molecules that
are not additives, but actual constituents of the antifouling
coating.
[0007] More recently, polyurethane-type polymers with a biocidal
activity have been developed. However, these polymers are obtained
by reacting hydroxy telechelic oligoisoprenes with isocyanates.
Aside from the recognized toxicity of the latter, the
polymerization reaction requires the addition of stannic catalysts,
which are prohibited in antifouling applications. Finally, the
implementation is more delicate and therefore presents a major
disadvantage in industrial use.
[0008] Another objective of this invention is to develop polymer
precursors not requiring a complex reaction to produce the polymer
coating, with simple and quick implementation, capable of being
performed on site.
[0009] The inventors have discovered that polymer films with
antifouling properties could be prepared from photo-cross-linkable
compositions based on certain telechelic oligoisoprenes.
[0010] To this end, the invention proposes a cross-linkable
antifouling composition, in particular an antibacterial, antifungal
and/or antalgic composition,
[0011] characterized in that it includes the combination of
[0012] at least one telechelic oligoisoprene of general formula
(I):
##STR00001##
[0013] or such an oligoisoprene (I) partially hydrogenated, of
formula (II):
##STR00002##
[0014] or a partially epoxidized compound of formula (I), of
formula (III):
##STR00003##
[0015] in which formulas: [0016] n is an integer between 5 and 100,
preferably between 8 and 70 [0017] m and p are integers, less than
n, preferably such that p.ltoreq.m.ltoreq.n [0018] R.sub.1 is a
group chosen from: OH, C.sub.1 to C.sub.12 alkoxy, preferably
C.sub.1 to C.sub.8 (for example, methyloxy, ethyloxy or octyloxy),
aryloxy (for example, phenyloxy), acryloyl, --NR.sub.3R.sub.4 with
R.sub.3 being H or a C.sub.1-C.sub.12 linear alkyl and R.sub.4
being H or a C.sub.1-C.sub.12 linear alkyl [0019] R.sub.2 is a
group chosen from: OH, acryloyl, --NR.sub.5R.sub.6 or
--N.sup.+R.sub.5R.sub.6R.sub.7 with R.sub.5 and R.sub.6, identical
or different, being chosen from: H, alkyl hydroxyalkyl, cyanoalkyl
and halogenoalkyl in C.sub.1-C.sub.12, in which R.sub.7 is a
C.sub.6-C.sub.15 linear alkyl,
[0020] and at least one cross-linking agent of said telechelic
oligoisoprene.
[0021] The oligoisoprene according to the invention is
advantageously in the form of a liquid at room temperature, namely
preferably between 5 and 35.degree. C. (or a range of possible
usage temperatures).
[0022] This oligoisoprene can be prepared from natural or synthetic
rubber, having the advantage of possessing microstructures that can
be chemically modified in a controlled manner. Its basic backbone
is linear cis-1,4-polyisoprene obtained from non-toxic compounds
(natural rubber). This cis-1,4-polyisoprene advantageously has a
functionality equal to 2.
[0023] It is thus capable of being spread on a support in a thin
layer, and, in the presence of a cross-linking agent, of
polymerizing by visible and/or ultraviolet radiation, forming a
flexible film.
[0024] It has been discovered that such a composition has biostatic
properties, i.e. inhibiting the proliferation of living organisms
on said surface, or biocidal properties, namely enabling any
biological organisms in contact with the surface of the support to
be destroyed.
[0025] The cross-linking agent is present in "catalytic"
proportions, i.e. in proportions preferably up to 5% by weight of
said compositions.
[0026] According to a first embodiment of the invention, in order
to adjust the viscosity of the composition according to the
invention and enable good spreading on the support, the latter may
also include a photo-cross-linkable reactive diluting agent,
advantageously under the same conditions as the oligoisoprene.
Examples of diluting agents are TMPO (2-ethyl-2-(hydroxymethyl)
oxetane) and HDDA (hexane diol diacrylate). This reactive diluting
agent enables a substantial increase in reactivity, i.e. the
polymerization rate which reduces the time and energy necessary to
produce a coating. In addition, this agent significantly reduces
the viscosity of the formulation, thereby facilitating its
application on the surface to be treated. It is present in
proportions of up to 40% by weight of the composition according to
the invention.
[0027] According to a second embodiment of the invention, the
composition does not contain a reactive diluting agent and consists
solely of the combination of at least said linear telechelic
oligoisoprene of formula (I), (II) or (III) and at least one
cross-linking agent of said telechelic oligoisoprene.
[0028] However, the composition can also contain "neutral"
constituents, i.e. not involved in the photo-cross-linking, such as
dyes, pigments, active principles, metal particles, magnetic
particles and reinforcing agents.
[0029] This invention also relates to an antifouling film,
characterized in that it is obtained by applying a thin film of the
liquid composition as described above onto a support and
cross-linked by visible and/or ultraviolet radiation. This
radiation can be provided by a continuous or discontinuous emission
lamp, emitting at wavelengths between around 200 nm and 800 nm.
[0030] The films thus obtained are transparent or translucent,
capable of being colored by the addition of pigments. In addition,
they can be flexible (elastic) or rigid according to the quantity
and nature of the diluent used. The surface roughness of the films
can be controlled by controlling the cross-linking speed, in
particular by means of the type of lamp used, by adjusting the
dilution rate and the viscosity. Indeed, the higher the
cross-linking speed, the greater the roughness of the film
formed.
[0031] The film obtained surprisingly has biocidal or biostatic
properties in particular with respect bacteria, fungi, microalgae
and/or macroalgae, regardless of the degree of roughness of the
surface. Such a film can thus coat surfaces intended to be
immersed, such as watercraft hulls.
[0032] This invention also relates to any support coated with a
film according to the present invention, in which the total
thickness of said film is less than one millimeter, and is
preferably between 10 .mu.m and 500 .mu.m.
[0033] Thus, the film according to the invention can advantageously
be used for antifouling protection of a support immersed in
freshwater or seawater, in particular watercraft hulls, in order to
inhibit the appearance of a biofilm on medical instruments,
catheters or implants, on walls in contact with an aqueous medium
or in a moist environment, such as floor covering surfaces,
external walls, pipelines, immersed apparatuses (in particular
immersed optical apparatuses) or cooling tours. This list is not
exhaustive.
[0034] This invention also relates to the use of the antifouling
composition described above, as an additive in the preparation of
materials, in order to confer bacteriostatic and/or bactericidal
properties thereon; or in the medical field, in particular in order
to produce medical instruments, biomaterials, catheters, prostheses
and implants; or to produce coverings, packaging containers, in
particular in the agrifood field.
[0035] This invention will be described in greater detail and
illustrated with the following non-limiting examples.
EXAMPLES
I. Photo-Cross-Linkable Oligoisoprene Syntheses
[0036] The synthesis of photo-cross-linkable precursors is
performed in a plurality of steps. First, the controlled
degradation of 100% linear cis-1,4-polyisoprene, with a
functionality equal to 2, provides access to a carbonyl telechelic
oligoisoprenes with a well defined number average molar mass and
chemical structure. Then, a plurality of chemical modifications on
these oligomers produce the various photo-cross-linkable
precursors.
[0037] All of the synthesized products are characterized by
.sup.1H-NMR, .sup.13C-NMR, IRTF, and Steric Exclusion
Chromatography.
Mode 1
I.1 Chemical Modifications of Carbonyl Telechelic
cis-1,4-polyisoprene (CTPI)
I.1.1 Examples 1 to 4
Reduction of Aldehyde and Ketone Ends: Synthesis of cis-1,4-hydroxy
Telechelic Polyisoprene (HTPI)
[0038] In a three-neck round-bottom flask equipped with a coolant
and magnetic stirring, the CIPI dissolved in THF (0.07 mol/L) is
added drop-by-drop to a sodium borohydride solution (NaBH.sub.4) in
THF (0.3 mol/L). The reaction mixture is then heated to 60.degree.
C. After 6 h, it is cooled and hydrolyzed with 20 g of ice
dissolved in 20 ml, of THF, poured drop-by-drop by means of an
adding ampoule. After a washing with a saturated sodium chloride
(NaCl) solution, the organic phase is dried with MgSO.sub.4,
filtered and concentrated with the rotary evaporator. The product
obtained is then dried in a vacuum.
[0039] The process conditions and yields obtained are presented in
table 1.
TABLE-US-00001 TABLE 1 NaBH.sub.4 T T Yield Examples CTPI (g)
(.degree. C.) (h) (%) 1 10 2.18 60 6 98 2 8 1.72 60 6 93 3 13 2.84
60 6 94 4 7 1.53 60 6 97
[0040] The .sup.1H-NMR of the product obtained (HTPI) gives:
##STR00004##
[0041] with a number average molar mass between 700 and 5000, in
which n is between 9 and 65.
I.1.2 Example 5
Hydrogenation of the HTPI: Synthesis of cis-1,4-hydrogenated
Polyisoprene (HHTPI)
[0042] In a catalytic hydrogenation device, 2 g of HTPI are
introduced, obtained according to one of examples 1 to 4, dissolved
in 50 mL of ethyl acetate and 500 mg of palladium supported on
carbon (Pd/C). The reaction mixture is subjected to mechanical
stirring under hydrogen pressure (3 bars). The time and temperature
of the reaction were varied so as to obtain different hydrogenation
rates (up to around 83%). The palladium is then separated by
filtration, the solution is concentrated with the rotary evaporator
and the final product is dried in a vacuum. The yield obtained is
75%.
[0043] The product obtained is characterized by .sup.1H-NMR:
##STR00005##
Mode 2
I.1.3 Examples 6 to 9
Synthesis of cis-1,4-amino Carbonyl Telechelic Polyisoprene from
CTPI
[0044] The reductive amination of the CTPI is performed selectively
on the aldehyde function only.
[0045] In a three-neck round-bottom flask equipped with magnetic
stirring and a coolant in an inert atmosphere, the CTPI in solution
is introduced into dichloromethane (0.03 mol/L) and amine (2.1
equivalents). Then, sodium triacetoxyborohydride (NaBH(OAc).sub.3)
(2.1 equivalents) is added to the solution. After 24 h at room
temperature, the mixture is washed with a soda solution (NaOH, 1N).
The organic phase is then separated, dried with MgSO.sub.4 and the
solvent is evaporated.
[0046] The process conditions and yields obtained are presented in
table 2.
TABLE-US-00002 TABLE 2 CTPI M.sub.CTPI Amine NaBH(OAc).sub.3 Yield
Examples (g) (g/mol) (mL) (g) (%) 6 8 1700 Diethyliminodi- 2.72 98
acetate: 1.73 7 5.42 1700 Diethylamine: 0.96 1.96 80 8 6 4500
Diethylamine: 0.41 0.83 90 9 12 4500 Diethanolamine: 1.56 85
0.53
[0047] The products obtained are, for example:
TABLE-US-00003 Amine used Product obtained ##STR00006##
##STR00007## ##STR00008## ##STR00009## ##STR00010##
##STR00011##
I.1.4 Examples 10 to 13
Reduction of Carbonyl Functions of Aminocarbonyl Telechelic
Oligoisoprenes
[0048] In a three-neck round-bottom flask in an inert atmosphere,
an etherate-aluminum lithium hydride solution (LiAlH.sub.4) at 1
mmol/mL (2 equivalents per polymer mole) is diluted in 10 mL of dry
ether. Then, the aminocarbonyl telechelic oligoisoprene dissolved
in anhydrous ether (0.01 mol/L) is added drop-by-drop. After 6 h
under stirring and at room temperature, the excess aluminum lithium
hydride is removed by hydrolysis and the product is extracted with
dichloromethane. Finally, the organic phase is separated, dried
with MgSO4 and the solvent is evaporated by means of a rotary
evaporator.
[0049] The details of the process and the yields obtained are
presented in table 3.
TABLE-US-00004 TABLE 3 Oligomer M.sub.oligomer LiAlH.sub.4 Yield
Examples (g) (g/mol) (mL) (%) 10 Oligomer 3 1700 6.2 90 (4.29) 11
Oligomer 1 1700 9.1 70 (7.91) 12 Oligomer 3 4500 2.38 88 (4.41) 13
Oligomer 2 4500 2.76 74 (5.12)
[0050] In particular, the following is obtained:
##STR00012##
I.1.5 Examples 14 and 15
Synthesis of .alpha.-Propyl Amino, .omega.-Amino Dihydroxyethyl
cis-1,4-polyisoprene from Oligoisoprene (2)
[0051] In a three-neck round-bottom flask in an inert atmosphere,
and equipped with magnetic stirring, oligoisoprene (2) dissolved in
dichloromethane (0.022 mol/L) and diethyl aminopropylamine (2.1
equivalents) is introduced. Then, sodium triacetoxyborohydride (2.1
equivalent(s) and glacial acetic acid (1 equivalent) are added. The
reaction is maintained for 24 h at room temperature. Finally, the
reaction mixture is washed with a soda solution (1 N) and the
organic phase is separated, dried on magnesium sulfate, filtered
and concentrated with the rotary evaporator.
[0052] The details of the process are presented in table 4:
TABLE-US-00005 TABLE 4 Oligomer Diethylamino- Acetic 2 propylamine
NaBH(OAc).sub.3 acid Yield Examples (g) (mL) (g) (mL) (%) 14 18
1.93 3.6 0.3 80 15 7.28 0.77 1.44 0.12 78
[0053] The .sup.1H-NMR gives:
##STR00013##
II.2.6 Examples 16 to 18
Partial Epoxidation of Telechelic Oligoisoprenes
[0054] Regardless of the telechelic oligomer to be epoxidized, the
process is the same. The amount of mCPBA needed is calculated by
using the following equation:
m.sub.mCPBA=(m.sub.oligomer)/68.8*(T.sub.e/100)*n*M.sub.mCPBA*(100/70)
[0055] with [0056] T.sub.e: Epoxidation rate [0057] (70/100):
Purity of in mCPBA [0058] (68.8): Molar mass of an isoprene unit
[0059] n: Number of isoprene patterns
[0060] The reaction is performed in a three-neck round-bottom flask
equipped with magnetic stirring and placed in an ice bath. The
oligomer dissolved in the dichloromethane (0.09 mol/L) is
introduced into the flask and left under stirring for 30 min to
reach a temperature of 0.degree. C. The desired amount of
epoxidation agent, in this case mCPBA (meta-chloroperbenzoic acid)
(according to the desired epoxidation rate) in solution in 20 mL of
CH.sub.2Cl.sub.2 is then added drop-by-drop to the oligomer
solution (see details in table 5). After the addition, the reaction
mixture is stirred for 3 h at room temperature, then washed with a
saturated sodium hydrogen carbonate solution. Finally, the organic
phase is dried on MgSO.sub.4, filtered and concentrated. The
concentrated product is dried in a vacuum for 24 h.
[0061] Concerning the aminotelechelic oligoisoprenes, washing with
5 N soda is performed after the reaction in order to regenerate the
amine. Indeed, during the reaction, the tertiary amine is
protonated.
TABLE-US-00006 TABLE 5 Oligomer 2 M.sub.oligomer mCPBA T.sub.e
Yield Examples (g) (g/ml) (g) (%) (%) 16 HTPI (4.35) 1700 1.46 10
95 17 HTPI (5) 4500 1.73 10 92 18 Oligomer 4 1700 1.73 10 89
(5)
[0062] The .sup.1H-NMR gives:
TABLE-US-00007 Starting product Product obtained HTPI ##STR00014##
HHTPI ##STR00015## oligomer 4 ##STR00016## oligomer 5
##STR00017##
II.2.7 Examples 19 to 22
Attachment of Acrylate Functions at the Chain Ends
[0063] In a three-necked round-bottom flask placed in a bath at
0.degree. C.; and under argon circulation, the oligomer is
introduced in solution in anhydrous dichloromethane (0.08 mol/L).
Then, triethylamine (2.3 equivalents, except for oligomer 5 (3.5
equivalents)) is added, then acryloyl chloride (2.3 equivalents,
except for oligomer 5 (3.5 equivalents)) is added drop-by-drop (see
details in table 6). The mixture is left under stirring and at room
temperature for 24 h. At the end of the reaction, it is washed with
a soda 1 N solution, then the organic phase is dried on magnesium
sulfate, filtered and concentrated. The product is dried in a
vacuum for 24 h.
TABLE-US-00008 TABLE 6 Acryloyl Oligomer chloride Triethylamine
Yield Examples (g) (mL) (mL) (%) 19 HTPI (7.25) 0.88 1.5 92 20
Oligomer 4 0.45 0.77 88 (3.86) 21 Oligomer 5 0.96 1.65 85 (5.52) 22
Oligomer 6 0.34 0.59 85 (3.20)
TABLE-US-00009 Starting product Product obtained HTPI ##STR00018##
HHTPI ##STR00019## EHTPI ##STR00020## oligomer 4 ##STR00021##
oligomer 5 ##STR00022## oligomer 6 ##STR00023##
[0064] .sup.1H-NMR:
I.1.8 Examples 23 to 25
Quaternization of Amine Functions of Aminotelechelic
Oligoisoprenes
[0065] In a three-necked round-bottom flask placed in a heating
bath, the oligomer to be treated (see table 7), dissolved in a
dichloromethane/acetonitrile (3/1) (0.02 mol/L), is introduced.
Then, the alkyl halogenide is added (5 equivalents/amine function)
and the reaction mixture is heated to 40.degree. C. in the case of
octyl iodide and to 65.degree. C. in the case of octyl bromide.
After 24 h, the solvents are evaporated with the rotary evaporator
and the excess alkyl halogenide is removed by high vacuum
evaporation.
TABLE-US-00010 TABLE 7 Oligomer Triethylamine Yield Examples (g)
(mL) (%) 23 oligomer 6 (4.2) 0.8 100 24 oligomer 11 (2.3) 0.55 100
25 oligomer 13 (10) 6.2 100
[0066] The .sup.1H-NMR gives:
##STR00024##
II. Example 26
Preparation of Coatings by Photo-Cross-Linking
[0067] The different coatings are prepared either by using only one
of the precursors described above or in the presence of reactive
diluents. Examples of some formulations are described in table 8
below.
TABLE-US-00011 TABLE 8 Formu- lation Photo-initiator Diluent
Photo-cross- No. Precursor (%)* (%)** linking mode 1 EHTPI Degacure
-- Cationic KI85 5% 2 EHTPI Degacure TMPO 30% Cationic KI85 5% 3
EHTPI + Degacure -- Cationic oligomer 14 KI85 5% (50/50) 4 oligomer
8 Darocur 1173 -- Free radical 3% 5 oligomers Darocur 1173 -- Free
radical (8 + 15) (50/50) 3% 6 oligomers Darocur 1173 -- Free
radical (8 + 15) (75/25) 3% 7 oligomers Darocur 1173 -- Free
radical (8 + 14) (50/50) 3% 8 oligomer 9 Darocur 1173 HDDA 30% Free
radical 3% *Mass percent with respect to the mass of the precursor
or precursor + diluent **Mass percent with respect to the total
mass of the mixture
[0068] The photo-initiators and diluents used in this example are
presented below:
##STR00025##
[0069] The formulations are spread on a support by means of Conway
bars, which makes it possible to control the thickness of the
coatings capable of ranging from 10 .mu.m to 500 .mu.m. The
irradiation intensities are 50 and 13 mW/cm.sup.2, respectively,
for the cationic and free radical polymerization.
[0070] In the conditions described above, the coatings obtained by
the free radical mode have roughnesses between 15 and 20 .ANG. and
those obtained by cationic mode have a greater roughness (between
40 and 45 .ANG.).
[0071] The supports, which are glass, metal or Plexiglas, were
tested.
[0072] The adhesion on these different surfaces was excellent, by
contrast with the comparative trials performed on
polyurethane-based films, which swelled in an aqueous medium and
separated from the supports.
Tests Evaluating Antifouling Properties
[0073] Formulations 1 to 8 above were tested with respect to marine
organisms which are indicators of biofouling and commonly used for
laboratory tests: bacteria, fungi, microalgae and macroalgae. Each
biological test was performed at least six times in order to ensure
the reputability of the results.
Placing the Coatings in Contact with the Bacteria
[0074] The marine bacteria selected for this work
(Pseudoalteromonas elyakovii Shewanella putrefaciens, Cobetia
marina, Polaribacter irgensil and Vibrio aestuarianus) are
recognized as major components of marine biofilms. The evaluation
of the potential antimicrobial activity of the formulations was
performed by the classic microplate method. The bacteria were
cultivated on the MHB medium (Mueller Hinton Broth, SIGMA) enriched
with NaCl (15 g/l). The films, cut by means of a punch, were
deposited in the wells of a microplate (Fisher, 96 wells). The
seeding of the microplates was then performed: 100 .mu.L of a
bacterial suspension containing 2.10.sup.8 cells/mL were deposited
in each well in a sterile manner. After incubation (48 h at
30.degree. C.), the antimicrobial activity was observed by
comparison of the bacterial growth between the formulations and the
control (C).
[0075] In the first screening series, three bacterial strains were
chosen (Pseudoalteromonas elyakovii, Shewanella putrefaciens,
Cobetia marina). The results presented in table 9 (first series of
tests) show, by comparison with the control, that formulations 1-3
and 5-7 enable inhibition of the growth of the three strains
tested. Formulations 4 and 8 have antibacterial properties with
respect to two of the three strains selected. This clearly
demonstrates the antibacterial character of the films of this
invention.
TABLE-US-00012 TABLE 9 1 2 3 4 5 6 7 8 C Pseudoalteromonas + + + -
+ + + + - elyakovii Shewanella + + + + + + + - - putrefacients
Cobetia marina + + + + + + + + -
[0076] A second series of tests was performed, in which the
bacteria presented in table 10 were placed in the presence of films
of formulation 1, 4 and 7 and the control.
[0077] A portion of films 4 and 7 was first subjected to an
"extraction", i.e. washing with dichloromethane at reflux at
40.degree. C. for 24 hours in order to remove any precursors
remaining on said films. The results obtained are presented in
table 10.
TABLE-US-00013 TABLE 10 4 (ex- 7 (ex- 1 4 traction) 7 traction) C
Pseudoalteromonas + + + + + - elyakovii Shewanella + + + + + -
putrefacients Cobetia marina + + + + + - Polaribacter + + + + + -
irgensii Vibrio + + + + + - aestuarianus
[0078] Key to Tables 9 and 10
[0079] Fi: no. film
[0080] C: control (reference surface: polystyrene)
[0081] (+): presence of an inhibition halo, zone in which the
bacteria do not cross over or under the film
[0082] (-): the bacteria, push over and/or under the films
[0083] No difference in efficacy was observed between films 4 and 7
subjected to extraction or not. The "antibacterial" action is not
therefore due to any presence of residues.
Placing the Films in Contact with the Microalgae
[0084] The phytoplanctonic algae selected (Amphora caffeaeformis,
Cylindrotheca closterium, Pleurochrysis roscoffensis,
Chlorarachnion globosum, Navicula jeffreyi and Exanthemachrysis
Gayraliae) were chosen for their importance in biofouling phenomena
in a seawater environment and for their capacity to form EPS
(exopolysaccharides playing a crucial role in the permanent
attachment of biofilms). The inhibition of their attachment and
growth is therefore a major challenge for the development of new
antifouling solutions.
[0085] The evaluation of the antimicroalgae potential of the
different films 1 to 8 was performed by the microplate method. The
strains are cultivated on the F/2 medium. The films cut by means of
a punch were deposited in the wells of a microplate (Fisher, 96
wells). The seeding of the microplates was then performed: 100
.mu.l of an algae suspension containing 1 .mu.g/mL of chlorophyll
were deposited in each well in a sterile manner. After incubation
(5 days at 25.degree. C.), the anti-microalgae activity was
observed by optical microscopy, and the count of the adhering
microalgae was performed on thirty different optical fields. The
average of the algae attached per surface unit is then
determined.
[0086] Table 11 below shows the percentage (%) of adhering cells on
the films with respect to the number of adhering cells on the
reference surface (C).
TABLE-US-00014 TABLE 11 1 2 3 4 5 6 7 8 C Amphora 4 6.3 2.36 2.1
1.1 1.2 1 4.2 100 coffeaeformis Cylindrotheca 3 4.6 2.75 2.3 1.07
0.76 0.95 3.76 100 closterium Pleurochrysis 4.2 4.5 1.44 1.85 1
0.87 0.7 4 100 Roscoffensis 5 Chlorarachnion 3.1 3.5 1.7 1 1.05 1.2
2.9 2.6 100 glosobosum Navicula jeffreyi 1.8 3 1.7 1.83 1.3 1.22
0.9 2 100 Exanthemachrysis 1.3 2 1.1 1.4 0.75 1.2 1 1.6 100
Gayraliae
Placing the Coatings in Contact with the Macroalgae
[0087] The algae used Ulva intestinalis, an opportunistic green
algae and one of the species most heavily involved in marine
fouling. It was collected the day of the tests on the coast of
Portsmouth (Great Britain).
[0088] The fertile parts (in sporulation) of the algae are selected
and placed in a Von Stosch medium. After several minutes, the
spores are released in the medium, and their presence is controlled
by observation with an optical microscope.
[0089] The polymer film samples are cut into small circles as above
and placed in a 96-well microplate. Then, 100 .mu.L of the medium
containing 25,000 spores are injected into each well (concentration
of 250,000 spores/mL). Empty wells are used as references (C) and
six replicates are produced for each sample. The plates are placed
in the dark for two hours in order to enable the spores to
attach.
[0090] After two hours, the wells are emptied and rinsed with the
Von Stosch solution in order to remove the unattached spores, then
100 .mu.L of the medium are added. The plates are placed in an
incubator at 15.degree. C., under illumination of 45 .mu.moles
photons m.sup.-2s.sup.-1 (photo-period: 16 hours of light/8 hours
of darkness) for one week.
[0091] The observations are performed by optical microscopy. The
count of attached spores as well as that of the germinated spores
were performed on thirty different optical fields. Averages of
attached/or germinated spores per surface unit are then determined
and presented in table 12.
Ulva intestinalis
TABLE-US-00015 TABLE 12 4 (ex- 7 (ex- Film 1 4 traction) 7
traction) C Adhering 3120 35 59 21 32 11800 spores/cm.sup.2
Percentage/ 27% 0.3% 0.5% 0.17% 0.27% 100% control Germinated 1090
0 0 0 0 9500 spores % spores 35% 0% 0% 0% 0% 85% germinated with
respect to fixed spores
[0092] By inhibiting almost all of the spore adhesion and the
germination thereof, films 4 and 7 appear to be excellent
anti-algae, with regard to Ulva intestinalis.
[0093] The adhesion and the growth of this algae is also strongly
inhibited on film no. 1.
Placing the Coatings in Contact with Fungi
[0094] The antifungal activity of the films was tested, using the
method described by Hellio et al. (2000, Appl. Microbiology and
Biotechnology, 54, 543-549), with regard to five marine fungal
strains of the culture collection of the University of Portsmouth
(School of Biological Sciences--Great Britain).
[0095] Halosphaeriopsis mediosetigera
[0096] Asteromyces cruciatus
[0097] Lulworthia uniseptata
[0098] Zalerion sp
[0099] Monodietys pelagica
[0100] The fungal strains were cultivated on inclined corn agar.
Each flexible film sample was incorporated in 200 .mu.L of corn
agar at 12%, pH 6 (Sigma). The test plate was inoculated in a
sterile medium at, the center with a pellet 2 mm in diameter of
agar containing mycelium. All of the tests were performed in
duplicate. After incubation at 25.degree. C. for four weeks, the
activity was evaluated by observing the growth of the fungal
colonies. The results are presented in table 13.
TABLE-US-00016 TABLE 13 4 (ex- 7 (ex- 1 4 traction) 7 traction) C
Halosphaeriopsis - + + + + - mediosetigera Asteromyces - + + + + -
cruciatus Lutworthia - + + + + - uniseptata Zalerion sp - + + + + -
Monodictys - + + + + - pelagica
[0101] -=normal growth=no differences with the control
[0102] +=inhibition of growth
[0103] Films 4 and 7 are also excellent antifungal agents.
* * * * *